Norbornyl pyridine derivatives, organoleptic uses of same, and the processes for preparing same

ABSTRACT

Described are norbornyl pyridine derivatives defined according to the generic structure: ##STR1## wherein R 5 , R 5  &#39;, R 5  &#34;, R 5  &#39;&#34; and R 5  &#34;&#34; each represents hydrogen or methyl with the proviso that at least four of R 5 , R 5  &#39;, R 5  &#34;, R 5  &#39;&#34; and R 5  &#34;&#34; represent hydrogen; wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond and wherein the pyridinyl moiety is bonded to the norbornyl moiety at the 2&#39; position of the norbornyl moiety and at either the 2 or the 4 position of the pyridinyl moiety as well as organoleptic uses thereof in augmenting or enhancing the aroma or taste of foodstuffs, chewing gums, toothpastes, chewing tobaccos, medicinal products, perfume compositions, colognes and perfumed articles including, but not limited to solid or liquid anionic, cationic, zwitterionic and nonionic detergents, cosmetic compositions, fabric softener compositions, fabric softener articles, hair preparations, and perfumed polymers. Also described are processes for preparing such compounds comprising reacting vinyl pyridines defined according to the structure: ##STR2## wherein one of R 1  or R 2  is hydrogen and the other of R 1  or R 2  is vinyl with a bicyclopentadiene derivative defined according to the structure: ##STR3## wherein R 3 , R 3  &#39;, R 3  &#34;, R 3  &#39;&#34; and R 3  &#34;&#34; each represents hydrogen or methyl with the proviso that at least four of R 3 , R 3  &#39;, R 3  &#34;, R 3  &#39;&#34; and R 3  &#34;&#34; represent hydrogen and wherein R 4 , R 4  &#39;, R 4  &#34;, R 4  &#39;&#34; and R 4  &#34;&#34; each represents hydrogen or methyl with at least four of R 4 , R 4  &#39;, R 4  &#34;, R 4  &#39;&#34; and R 4  &#34;&#34; representing hydrogen and then as desired hydrogenating the resulting product.

BACKGROUND OF THE INVENTION

There is a continuing search for materials having desirable fragranceand organoleptic properties. Such materials are sought either to replacecostly natural materials or to provide new food flavors, fragrances,perfume types or flavor nuances which have not, heretofore, beenavailable.

Especially desirable qualities for substances having interestingfragrances and flavors are stability in a wide variety of perfumedarticles, perfume compositions and foodstuffs, ease of manufacture,intensity and pleasantness of aroma and intensity of pleasantness offlavor.

Particularly desirable are in the perfume, cologne and perfumed articlearea are fragrance nuances which can be described as petitgrain-like,neroli-like, verdima-like, green, herbaceous, galbanum-like, musk,amber, woody, rose, minty, cedarleaf, eucalyptus, bergamot, orris-likeand balsamic-like with amber-like, woody, musk, rose, green, herbaceous,leafy, minty and vanoris-like undertones.

Particularly desirable in the food flavor, chewing gum flavor,toothpaste flavor, medicinal product flavor and chewing tobacco flavorareas are flavors which can be described as bell pepper-like, greenvegetable, galbanum-like, floral, pear-like, peach-like, walnut-like,green, orange-albedo, minty, cinnamon-like and bitter chocolate-like,insofar as their aromas and tastes are concerned.

Terpinyl pyridine derivatives have been previously described in theorganoleptic industry, for example, U.S. Pat. No. 3,716,543 issued onFeb. 13, 1973 discloses compounds defined according to the structures:##STR4## and implicitly includes in its genus the compound having thestructure: ##STR5## Norbornyl pyridine derivatives defined according tothe structures: ##STR6## are disclosed as intermediates useful for thepreparation of hypotensive agents which are bisquaternary ammoniumsalts.

Nothing in the prior art, however, discloses the genus of compoundsdefined according to the structure: ##STR7## wherein the dashed linerepresents a carbon-carbon single bond or a carbon-carbon double bondand wherein R₅, R₅ ', R₅ ", R₅ '" and R₅ "" represents hydrogen ormethyl with at least four of R₅, R₅ ', R₅ ", R₅ '" and R₅ "" beinghydrogen and wherein the bond between the pyridinyl moiety and thenorbornyl moiety leading from the 2' position of the norbornyl moiety islocated at the pyridinyl moiety at either the 2 position or the 4position thereof for augmenting or enhancing the aroma or taste offoodstuffs, chewing gums, chewing tobaccos, toothpastes, medicinalproducts, perfume compositions, colognes and perfumed articles. Nothingin the prior art discloses such compounds as useful as hypotensiveagents and as anti-stress agents.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the crude reaction product of Example Icontaining the compound having the structure: ##STR8## (Conditions:SE-30 column programmed at 100°-220° C. at 8° C. per minute).

FIG. 2 is the NMR spectrum for the compound having the structure:##STR9## produced according to Example I ("endo":"exo" isomer ratioabout 55:45. Conditions: Field strength: 100 MHz; solvent: CFCl₃).

FIG. 3 is the GLC profile for the crude reaction product of Example IIcontaining the compound having the structure: ##STR10## (Conditions:Carbowax column programmed at 100°-220° C. at 8° C. per minute).

FIG. 4 is the NMR spectrum for fraction 1 of the distillation product ofthe reaction product of Example II containing the compound having thestructure: ##STR11## (Conditions: Field strength: 100 MHz; solvent:CFCl₃).

FIG. 5 is the GLC profile for the crude reaction product of Example IIIcontaining the compound having the structure: ##STR12## (Conditions:SE-30 column programmed at 100°-220° C. at 8° C. per minute).

FIG. 6 is the NMR spectrum for fraction 6 of the distillation product ofthe reaction product of Example III containing the compound having thestructure: ##STR13## (Conditions: Field strength: 100 MHz; solvent:CFCl₃).

FIG. 7 is the GLC profile for the crude reaction product of Example IVcontaining the compound having the structure: ##STR14## (Conditions:Carbowax column programmed at 100°-220° C. at 8° C. per minute).

FIG. 8 is the NMR spectrum for the compound having the structure:##STR15## produced according to Example IV (Conditions: Field strength100 MHz; solvent: CFCl₃).

FIG. 9 is the GLC profile for the crude reaction product of Example Vcontaining a mixture of compounds defined according to the structures:##STR16## or broadly defined according to the structure: ##STR17##

FIG. 10 is the NMR spectrum for the mixture of compounds definedaccording to the structure: ##STR18## produced according to Example V(Conditions: Solvent: CFCl₃ ; field strength: 100 MHz).

FIG. 11 is the GLC profile for the crude reaction product of Example VIcontaining a mixture of compounds defined according to the structure:##STR19## (Conditions: SE 30 column programmed at 100°-220° C. at 8° C.per minute).

FIG. 12 is the NMR spectrum for fraction 5 of the distillation productof the reaction product of Example VI containing a mixture of compoundsdefined according to the structure: ##STR20## (Conditions: Fieldstrength: 100 MHz; solvent: CFCl₃).

FIG. 13 is a partial side elevation and partial sectional view of anapparatus for forming polymer pellets centered with at least one of thenorbornyl pyridine derivatives of our invention.

FIG. 14 is a section taken on the line 14--14 of FIG. 13.

DETAILED DESCRIPTION OF THE DRAWINGS

Referring to FIGS. 13 and 14 in particular, the apparatus used inproducing polymeric fragrances containing the norbornyl pyridinederivatives of our invention comprises a device for forming scentedpolyolefin (for example) pellets which comprises a vat or container 2101into which a mixture of polyolefin such as polyethylene and an aromaticsubstance or scented material is placed (in this case at least one ofthe norbornyl pyridine derivatives of our invention). The container isclosed by an airtight lid 228 and clamped to the container by bolts 265.A stirrer 273 traverses the lid or cover 228 in airtight manner and isrotated in a suitable manner. A surrounding cylinder 212 having heatingcoils which are supplied with electric current through cable 224 from arheostat or control 216 is operated to maintain a temperature inside thecontainer 2101 such that polyethylene or other thermoplastic polymer inthe container will be maintained in the molten or liquid state. It hasbeen found advantageous to employ a colorless odorless polymer (e.g.,polyethylene) with a viscosity ranging between 180 and 220 sayboltseconds and having a melting point in the range of 200°-280° F. Theheater 2201 is operated to maintain the upper portion of the container2101 within a temperature range of from 250°-350° F. The bottom portionof the container 218 is heated by means of heating coils 222 heatedthrough a control 220 connected thereto through a connecting wire 226 tomaintain a lower portion of the container 218 within a temperature rangeof from 250°-350° F.

Thus, polymer (e.g., polyethylene) is added to container 2101 and isheated from 10-12 hours whereafter a scented aroma imparting material(at least one of the norbornyl pyridine derivatives of our invention) isadded quickly to the melt. The material must be compatible withpolyolefin and forms a homogeneous liquid melt therewith. The scentedmaterial is of a type for the particular aroma desired and formulatedspecifically for the scenting purpose for which the polyolefin will beemployed.

Generally, about 5-30% by weight of the scented material (at least oneof the norbornyl pyridine derivatives of our invention) are added to thepolyolefin.

After the scent imparting material (e.g., one of the norbornyl pyridinederivatives of our invention) is added to container 2101, the mixture isstirred for a few minutes for example, 5-15 minutes and maintainedwithin the temperature range as indicated previously by the heatingcoils 212 and 218, respectively. The controls 216 and 220 are connectedthrough cables 224 and 226 to a suitable power supply of electriccurrent for supplying the power for heating purposes.

Thereafter, the valve "V" is opened permitting the mass to flowoutwardly through conduit 232 having a multiplicity of orifices 234adjacent to the lower side thereof. The outer end of the conduit 232 isclosed so that the liquid polymer (e.g., polyolefin) and aroma mixturewill continuously drop through orifices 234 downwardly from the conduit232. During this time, the temperature of the polymer (e.g., polyolefin)and aroma mixture in the container 2101 (e.g., one of the norbornylpyridine derivatives of our invention) is accurately controlled so thata temperature in the range of from about 210°-275° F. will exist in theconduit 232. The regulation of the temperature through the control 216and the control 2201 is essential in order to insure temperature balanceto provide for the continuous dropping or dripping of molten polymer(e.g., polyethylene) and scenting material (e.g., one or more of thenorbornyl pyridine derivatives of our invention) mixture through theorifices 234 at a rate which will insure the formation of droplets 236which will fall downwardly onto a moving conveyor belt 238 trained torun between conveyor wheels 240 and 242 beneath the conduit 232.

When the droplets 236 fall onto the conveyor 238 they form pellets 244which harden almost instantaneously and fall off the end of the conveyor238 into a container 259 which is advantageously filled with water orsome other suitable cooling liquid to insure the rapid cooling of eachof the pellets. The pellets 244 are then collected from the container259 and utilized in processes as illustrated infra.

A feature of this aspect of the process of our invention is theprovision for moistening the conveyor belts 238 to insure rapidformation of the solid polymer (e.g., polyolefin) scented pellets 244without sticking to the belt. The belt 238 is advantageously of amaterial which will not normally stick to a melted plastic but amoistening means 248 insures a sufficiently cold temperature of the beltsurface for adequate formation of the pellets 244. The moistening meanscomprises a container 259 which is continuously fed with water 252 tomaintain a level 254 for moistening a sponge element 256 which bearsagainst the exterior surface of the belt 238.

THE INVENTION

The invention comprises the novel product as well as novel processesaccording to which such products are manufactured, this specificembodiments of which are described hereinafter by way of example and inaccordance with which it is now preferred to practice the invention.

Briefly, the present invention provides norbornyl pyridine derivativesdefined according to the generic structure: ##STR21## wherein the dashedline represents a carbon-carbon single bond or a carbon-carbon doublebond and R₅, R₅ ', R₅ ", R₅ '" and R₅ "" each represents hydrogen ormethyl with a proviso that at least four of R₅, R₅ ', R₅ ", R₅ '" and R₅"" represent hydrogen; and wherein the bond joining the pyridinyl moietywith the norbornyl moiety at the 2' position of the norbornyl moiety islocated at either the 2 position or the 4 position of the pyridine ringuseful in augmenting or enhancing the aroma or taste of consumablematerials including perfume compositions, colognes and perfumedarticles; foodstuffs, chewing gums, toothpastes, medicinal products andchewing tobaccos.

The compound defined according to the structure: ##STR22## wherein thedashed line represents a carbon-carbon single bond or wherein the dashedline represents a carbon-carbon double bond and one of R₅, R₅ ', R₅ ",R₅ '" and R₅ "" is methyl are novel compounds.

The norbornyl pyridine derivatives of our invention augment or enhancethe aroma of perfume compositions, colognes and perfumed articles byaugmenting or enhancing petitgrain-like, neroli-like, verdima-like,green, herbaceous, galbanum-like, musk, amber, woody, rose, minty,cedarleaf, eucalyptus, bergamot, orris-like and balsamic-like withamber-like, woody, musk, rose, green, herbaceous, leafy, minty andvanoris-like undertones.

The norbornyl pyridine derivatives of our invention also augment orenhance bell pepper-like, green vegetable, galbanum-like, floral,pear-like, peach-like, orange-albedo, minty, cinnamon-like and bitterchocolate-like aroma and taste nuances in foodstuffs, chewing gums,toothpastes, medicinal products and chewing tobaccos.

Examples of the norbornyl pyridine derivatives of our invention andtheir organoleptic properties are set forth in the following Table I:

                                      TABLE I                                     __________________________________________________________________________    NORBORNYL PYRIDINE DERIVATIVES                                                OF OUR INVENTION           PERFUME PROPERTY   FLAVOR PROPERTY                 __________________________________________________________________________    Compound having the structure:                                                                           A petitgrain-like, neroli-like,                                                                  A bell pepper, green                                                          vegetable,                       ##STR23##                 verdima-like, green, herbaceous, galbanum-like                                aroma with amber- like undertones.                                                               galbanum and floral-like                                                      aroma and taste profile at                                                    0.1 ppm causing it to be                                                      useful in green vegetable                                                     and bell pepper flavors.        produced according to Example I.                                              Compound having the structure:                                                                           A musk and amber aroma with woody undertones.                                                    A pear-like, peach-like and                                                   alnut-like aroma and taste                                                    profile at 5 ppm.                ##STR24##                                                                    produced according to Example II.                                             Compound having the structure:                                                                           A woody aroma with musk, amber and rose                                       undertones.        A pear-like, peach-like and                                                   wal- nut-like aroma and                                                       taste profile at 2 ppm.          ##STR25##                                                                    produced according to Example III                                             Compound having the structure:                                                                           A petitgrain and rose aroma profile with                                      woody, musk and amber undertones.                                                                An orange-albedo aroma and                                                    taste profile at 20 ppm                                                       causing it to be useful in                                                    fresh orange                                                                  jucie flavors.                   ##STR26##                                                                    produced according to Example IV                                              Mixture of compounds having the structure:                                                               A green, herbaceous, minty, cedarleaf,                                        eucalyptus and bergamot aroma with green,                                     herbaceous, leafy and minty nuances on dry                                    out.               A fresh natural green,                                                        natural orange-albedo                                                         character at 0.5 ppm.            ##STR27##                                                                    produced according to Example V                                               Mixture of compounds defined according to the structure:                                                 A green, woody, cinnamon-like, orris-like and                                 balsamic aroma profile with vanoris-like                                      undertones.        A cinnamon and bitter                                                         chocolate aroma and taste                                                     profile at 0.1 ppm.              ##STR28##                                                                    produced according to Example VI                                              __________________________________________________________________________

The norbornyl pyridine derivatives of our invention are produced byreacting a vinyl pyridine defined according to the structure: ##STR29##where one of R₁ or R₂ is vinyl and the other of R₁ or R₂ is hydrogenwith bicyclopentadiene compound defined according to the structure:##STR30## wherein R₃, R₃ ', R₃ ", R₃ '" and R₃ "" represent hydrogen ormethyl with at least four of R₃, R₃ ', R₃ ", R₃ '" and R₃ "" beinghydrogen and wherein R₄, R₄ ', R₄ ", R₄ '" and R₄ "" each representsmethyl or hydrogen with at least four of R₄, R₄ ', R₄ ", R₄ '" and R₄ ""being hydrogen according to the reaction: ##STR31## The resultingcompound may be used "as-is" for its organoleptic properties or it maybe further reacted with hydrogen using a hydrogenation catalystaccording to the reaction: ##STR32## wherein R₅, R₅ ', R₅ ", R₅ '" andR₅ "" each represents hydrogen or methyl with at least four of R₅, R₅ ',R₅ ", R₅ '" and R₅ "" representing hydrogen.

More specifically, the reaction of the bicyclopentadiene moiety with thevinyl pyridine takes place at reflux conditions in the absence ofsolvent with a mole ratio of bicylopentadiene derivative:vinyl pyridinederivative being approximately 1:1 with a slight excess ofdicylopentadiene derivative. The reaction time may vary from about threehours up to about 15 hours; the reaction temperature may vary from about140° C. up to about 180° C. with the reaction temperature beingdependent upon the reactants employed and the pressure of reaction. Itis most convenient and preferable to carry out the reaction atatmospheric pressures but pressures above atmospheric or belowatmospheric may be utilized without substantially affecting the yield ofreaction product. The reaction is preferably carried out in the presenceof an Ionox® catalyst. Ionox® is p-t-butyl catechol.

At the end of the reaction, the reaction mass may be "worked up" usingthe standard procedures and subsequently distilled as by means offractional distillation. The resulting product may be used "as-is" forits organoleptic properties or it may be further reacted with hydrogen.The reaction takes place in the presence of an inert solvent such asisopropyl alcohol at a temperature in the range of from about 25° C. upto about 100° C. and at a pressure in the range of from about 400 psigup to about 1500 psig. The reaction is necessarily carried out in areactor that is equipped to withstand such pressures and temperatures.The reaction time may vary between about five hours and 20 hours,depending upon the yield of desired hydrogenated product. In certaininstances it is useful to obtain a low yield of hydrogenated product andretain the mixture of hydrogenated and unhydrogenated derivative havingthe structures: ##STR33## The proportion of hydrogenated tounhydrogenated derivative being determinative of the particularorganoleptic properties sought in the resulting reaction product. Thehydrogenation is carried out using standard hydrogenation techniques anda hydrogenation catalyst such as palladium-on-carbon (e.g., 5-15%palladium-on-carbon), palladium-on-calcium carbonate and Raney nickel.

The hydrogenation reaction: ##STR34## is carried out utilizing standardhydrogenation techniques and a hydrogenation catalyst such aspalladium-on-carbon (e.g., 5-15% palladium-on-carbon) at temperatures ofbetween 130°-170° C. and pressures of between 40 and 250 psig.

When the norbornyl pyridine derivatives of our invention are used asfood flavor adjuvants, the nature of the co-ingredients included withthe norbornyl pyridine derivatives used in formulating the productcomposition will also serve to alter, modify, augment or enhance theorganoleptic characteristics of the ultimate foodstuff treatedtherewith.

As used herein, in regard to flavors, the terms "alter", "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, chewing gums, vegetables, cereals, soft drinks,snacks and the like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrup, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble, chewable plastic gum base such aschickle, or substitutes therefor, including jelutong, guttakay, rubberor certain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine; and a flavoring composition whichincludes one or more of the norbornyl pyridine derivatives of ourinvention, and in addition, sweetening agents which may be sugars,including sucrose or dextrose and/or artificial sweeteners such ascyclamates or saccharin. Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials may,in general, be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxy-anisole (mixture of 2- and3-tertiary-butyl-4-hydroxy-anisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth, guar gum and xantan gum; gelatin, proteinaceousmaterials; lipids; carbohydrates; starches, pectins and emulsifiers,e.g., mono- and diglycerides of fatty acids, skim milk powder, hexoses,pentoses, disaccharides, e.g., sucrose, corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, palmitic acid, myristic acid and the like, mono- anddiglycerides of fatty acids, lecithin, defoaming and flavor-dispersingagents such as sorbitan monostearate, potassium stearate, hydrogenatedtallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anticaking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and favor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methyl butanal,beta, beta-dimethylacrolein, methyl-n-amyl ketone, n-hexenal, 2-hexenal,isopentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2-heptanal, nonylaldehyde, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,methyl-3-butanone, benzaldehyde, damascone, damascenone, acetophenone,2-heptanone, o-hydroxyacetophenone, 2-methyl-2-hepten-6-one, 2-cotanone,2-undecanone, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal,2-phenyl-2-pentenal, furfural, 5-methyl furfural, cinnamaldehyde,beta-cyclohomocitral, 2-pentanone, 2-pentenal and propanal; alcoholssuch as 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol,ethanol, geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-1,cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate, eugenol,linalool, 2-heptanol, acetoin; esters, such as butyl acetate, ethylacetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myrsitate, ethyl alpha-methylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as dimethyl naphthalene, dodecane, methyl diphenyl, methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane, tetramethylnaphthalene, tridecane, trimethyl naphthalene, undecane, caryophylene,1-phellandrene, p-cymene, 1-alphapinene; pyrazines, such as2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, 2-methoxy-3 -isobutyl pyrazine, tetramethylpyrazine,trimethylpyrazine; essential oils, such as jasmine absolute, cassia oil,cinnamon bark oil, rose absolute, orris absolute, lemon essential oil,Bulgarian rose, yara yara and vanilla; lactones, such as δ-nonalctone;sulfides, e.g., methyl sulfide and other materials such as maltol,acetoin and acetals (e.g., 1,1-diethoxyethane, 1,1-dimethoxyethane anddimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the norbornyl pyridinederivatives of our invention by not covering or spoiling theorganoleptic properties (aroma and/or taste) thereof; (ii) benon-reactive with the norbornyl pyridine derivatives of our inventionand (iii) be capable of providing an environment in which the norbornylpyridine derivatives of our invention can be dispersed or admixed toprovide a homogeneous medium.

In addition, selection of one or more flavoring adjuvants, as well asthe quantities thereof, will depend upon the precise organolepticcharacter desired in the finished product. Thus, in the case offlavoring compositions, ingredient selection will vary in accordancewith the foodstuff, chewing gum, medicinal product, toothpaste orchewing tobacco to which the flavor and/or aroma are to be imparted,modified, altered or enhanced. In contradistinction, in the preparationof solid products, e.g., simulated foodstuffs, ingredients capable ofproviding normally solid compositions should be selected such as variouscellulose derivatives.

As will be appreciated by those skilled in the art, the amount of thenorbornyl pyridine derivatives employed in a particular instance canvary over a relatively wide range, depending upon the desiredorganoleptic effects to be achieved. Thus, correspondingly greateramounts would be necessary in those instances wherein the ultimate foodcomposition to be flavored is relatively bland to the taste, whereasrelatively minor quantities may suffice for purposes of enhancing thecomposition merely deficient in natural flavor or aroma. The primaryrequirement is that the amount selected be effective, i.e., sufficientto alter, modify or enhance the organoleptic characteristics of theparent composition, whether foodstuff per se, chewing gum per se,medicinal product per se, toothpaste per se, or flavoring composition.

The use of insufficient quantities of the norbornyl pyridine derivativesof our invention will, of course, substantially vitiate any possibilityof obtaining the desired results while excess quantities proveneedlessly costly and in extreme cases, may disrupt the flavor-aromabalance, thus proving self-defeating. Accordingly, the terminology"effective amount" and "sufficient amount" is to be accorded asignificance in the context of the present invention consitent with theobtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions, chewing tobaccocompositions, chewing gum compositions and toothpaste compositions, itis found that quantities of norbornyl pyridine derivatives ranging froma small but effective amount, e.g., 0.5 parts per million up to about100 parts per million based on total composition are suitable.Concentrations in excess of the maximum quantity stated are not normallyrecommended, since they fail to provide commensurate enhancement oforganoleptic properties. In those instances wherein the norbornylpyridine derivatives of our invention are added to the foodstuff as anintegral component of a flavoring composition, it is, of course,essential that the total quantity of flavoring composition employed besufficient to yield an effective concentration of norbornyl pyridinederivatives in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the norbornyl pyridine derivatives inconcentrations ranging from about 0.1% up to about 15% by weight basedon the total weight of the said flavoring composition.

The compositions described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the norbornyl pyridine derivatives ofour invention with, for example, gum arabic, gum tragacanth, guar gum,xanthan gum, carrageenan and the like, and thereafter spray-drying theresultant mixture whereby to obtain the particulate solid product.Pre-prepared flavor mixes in powder form, e.g., a fruit-flavored powdermix, are obtained by mixing the dried solid components, e.g., starch,sugar and the like and one or more of the norbornyl pyridine derivativesof our invention in a dry blender until the requisite degree ofuniformity is achieved.

It is presently preferred to combine with the norbornyl pyridinederivatives of our invention, the following adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Cassia Oil;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Eugenol;

Vanillin;

Caryophyllene;

Methyl cinnamate;

Guiacol;

Ethyl pelargonate;

Cinnamaldehyde;

Methyl Anthranilate;

5-Methyl furfural;

Isoamyl acetate;

Isobutyl acetate;

Cuminaldehyde;

Alpha ionone;

Cinnamyl formate;

Ethyl butyrate;

Methyl cinnamate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Furfural;

Ethyl acetate;

Anethole;

2,3-Dimethyl pyrazine;

2-Ethyl-3-methyl pyrazine;

3-Phenyl-4-pentenal;

2-Phenyl-2-hexenal;

2-Phenyl-2-pentenal;

3-Phenyl-4-pentenal diethyl acetal;

β-Damascone(1-crotonyl-2,2,6-trimethylcyclohex-1-ene);

β-Damascenone(1-crotonyl-2,2,6-trimethylcyclohex-1-ene);

Beta-cyclohomocitral(2,2,6-trimethylcyclohex-1-ene carboxaldehyde;

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentneoic acid;

Elemecine(4-allyl-1,2,6-trimethoxybenzene);

Isoelemecine(4-propenyl-1,2,6-trimethoxybenzene);

2-(4-Hydorxy-4-methylpentyl)norbornadiene;

2-Methoxy-3 isobutyl pyrazine;

Methylmercaptan;

β-Ionone;

2,4-Decadienal;

2,6-cis-Nonadienal;

Ethyl-2-methylbutyrate;

Amyl acetate; and

Benzaldehyde.

The norbornyl pyridine derivatives of our invention and one or moreauxiliary perfume ingredients, including for example, alcohols,aldehydes, ketones, terpinic hydrocarbons, nitriles, esters, aminesother than the norbornyl pyridine derivatives of our invention, naturalsynthetic oils and synthetic essential oils may be admixed so that thecombined odors of the individual components produce a pleasant anddesired fragrance, particularly and preferably in the floral, musk,woody, rose, herbaceous and minty and orris fragrances.

Such perfume compositions usually contain (a) the main note or the"bouquet" or foundation stone of the composition; (b) modifiers whichround off and accompany the main note; (c) fixatives which includeodorous compositions which lend a particular note to the perfumethroughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however, theover-all sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, the norbornylpyridine derivatives of our invention can be used to alter, modify orenhance the aroma characteristics of a perfume composition, for example,by utilizing or moderating the olfactory reaction contributed by anotheringredient in the composition.

The amount of the norbornyl pyridine derivatives of our invention whichwill be effective in perfume compositions as well as in perfumedarticles and colognes depends on many factors, including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as 0.01% ofthe norbornyl pyridine derivatives of our invention or even less (e.g.,0.005%) can be used to impart, augment or enhance petitgrain-like,neroli-like, verdima-like, green, herbaceous, galbanum-like, musk,amber, woody, rose, minty, cedarleaf, eucalyptus, bergamot,cinnamon-like, orris-like, and balsamic-like with amber-like, woody,musk, rose, green, herbaceous, leafy, minty and vanoris-like undertonesto soaps, cosmetics or other products. The amount employed can range upto 70% of the fragrance components and will depend on consideration ofcost, nature of the end product, the effect desired on the finishedproduct and the particular fragrance sought.

The norbornyl pyridine derivatives of our invention are useful (takenalone or together with other ingredients in perfume compositions) as(an) olfactory component(s) in detergents and soaps, space odorants anddeodorants, perfumes, colognes, toilet water, bath preparations, such ascreams, deodorants, hand lotions and sun screens; powders, such astalcs, dusting powders, face powders and the like. When used as (an)olfactory component(s) in perfumed articles as little as 0.1% of thenorbornyl pyridine derivatives of our invention or compositioncontaining a high proportion of the norbornyl pyridine derivatives ofour invention will suffice to impart, augment or enhance intense longlasting petitgrain-like, neroli-like, verdima-like, green, herbaceous,galbanum-like, musk, amber, woody, rose, minty, cedarleaf, eucalyptus,bergamot, cinnamon-like, orris-like, and balsamic aromas withamber-like, woody, rose, musk, rose, green, herbaceous, leafy, minty andvanoris-like undertones.

The range of norbornyl pyridine derivatives of our invention useful inperfumed articles including solid or liquid anionic, cationic, nonionicand zwitterionic detergents, soaps, space odorants and deodorants, bathpreparations, such as creams, deodorants, hand lotions and sun screens;powders, such as talcs, dusting powders, face powders and the like andperfumed polymers may vary from as little as 0.1% to as much as 5% ofthe norbornyl pyridine derivatives of our invention.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle or carrier for the norbornyl pyridinederivatives or composition containing norbornyl pyridine derivatives ofour invention. The vehicle can be a liquid, such as an alcohol, such asethyl alcohol, a non-toxic glycol, such as propylene glycol or the like.The carrier can also be an absorbent solid, such as gum (i.e., gumarabic, guar gum, xanthan gum or the like) or components forencapsulating the composition (such as gelatin when encapsulation iscarried out by means of coacervation or such as a urea formaldehydeprepolymer when encapsulation is carried out by forming a polymeric wallaround a liquid perfume scenter).

It is well known in the tobacco art that the domestic tobaccos which areexemplified by burley, Maryland, flue-cured, bright leaf or Virginiatobaccos are low in flavor as compared with so-called oriental oraromatic tobaccos which are imported from Turkey, Greece, Bulgaria,Yugoslavia, Rhodesia, and Russia. Accordingly, it has been commonpractice in the tobacco industry to prepare blends of domestic andoriental tobaccos in order to provide cigarettes which have desiredflavor and aroma characteristics. This invention also provides a tobaccowhich has an enhanced flavor and aroma.

With reference to this aspect of our invention which concerns tobaccoflavoring, the norbornyl pyridine derivatives of our invention are addedto tobacco in amounts to provide generally a tobacco in which isdispersed about 0.00005 to about 0.3 percent by weight of the additive.Preferably, the amount of additive is between about 0.0003 and about0.02 percent by weight in order to provide tobacco having a desiredflavor and aroma. The preferred percentages may be somewhat less,however, if other flavorants imparting a desired aroma are alsoemployed. The additives may be applied in any suitable manner andpreferably in the form of a liquid solution or suspension by spraying,dipping or otherwise. The additives may be incorporated at any step inthe treatment of tobacco, but are preferably added after aging; curingand shredding and before the tobacco is formed into tobacco productssuch as cigarettes, cigars and the like. Likewise, it will be apparentthat only a portion of the tobacco need be treated and the thus treatedtobacco may be blended with other tobacco before the tobacco productsare formed. In such cases, the tobacco treated may have the additives,in excess of the amounts above indicated so that when blended with othertobaccos the final product will have the percentage within the indicatedrange.

In accordance with one example of this invention, an aged, cured andshredded domestic burley tobacco is sprayed with a one percent ethylalcohol solution of a mixture of compounds defined according to thestructure: ##STR35## (produced according to Example VI, infra) in anamount to provide a tobacco composition containing a 0.005 percent byweight of the norbornyl pyridine derivatives of our invention on a drybasis. Thereafter, the alcohol is removed by evaporation and the tobaccois manufactured into cigarettes by the usual techniques. The cigarette,when treated as indicated, has a desired and pleasing aroma which isdetectable in the main and side smoke streams when the cigarette issmoked; this aroma is described by some smokers as a woody cigarbox-like note with pleasant cinnamon and oriental-like nuances in theafter-taste.

It will be particularly apparent that the manner in which the norbornylpyridine derivatives of our invention are applied to the tobacco is notparticularly important since, as indicated it may be done in the form ofspraying or dipping, utilizing suitable suspensions or solutions of theadditive.

Thus, water or volatile organic solvents, such as alcohol, ether,acetone, volatile hydrocarbons and the like, may be used as the carryingmedium for the additive while it is being applied to the tobacco. Also,other flavor and aroma producing additives, such as those disclosed inJones, U.S. Pat. No. 2,766,145, the specification of which isincorporated by reference herein, and Schumacher, U.S. Pat. No.2,978,365, the specification of which is incorporated by referenceherein, may be incorporated into the tobacco with the additives of thisinvention.

While this invention is useful in the manufacture of cigarette tobacco,it is also suitable for use in connection with the manufacture of pipetobacco, cigars and other tobacco products formed from sheeted tobaccodust or fines which are well known in the art. Likewise, the additivesof the invention can be incorporated with materials such as filter tipmaterials, seam paste, packaging materials and the like which are usedalong with the tobacco to form a product adapted for smoking.Furthermore, the compounds can be added to certain tobacco substitutesof natural or synthetic origin and by the term "tobacco" as usedthroughout this specification is meant any composition intended forhuman consumption by smoking or otherwise, whether composed of tobaccoplant parts, substitute materials or both.

The following Examples I-VI serve to illustrate methods for preparationof the norbornyl pyridine derivatives of our invention. The followingExamples VII et seq show methods for utilizing the organolepticproperties of the norbornyl pyridine derivatives of our invention. Itwill be understood that these examples are illustrative and theinvention is to be considered as restricted thereto only as indicated inthe appended claims.

EXAMPLE I Preparation of Vinyl Pyridine Dicyclopentadiene Adduct##STR36##

Into a 2 liter reaction vessel equipped with stirrer thermometer, refluxcondenser and thermometer are placed the following materials:

500 grams vinyl pyridine (4.76 moles)

660 grams dicyclopentadiene (5.0 moles)

10 grams Ionox®

With stirring, the mixture is heated to reflux (147°-158° C.) andrefluxed for a period of eight hours. At the end of the reaction, thereaction mass is charged to a splash column packed with saddles anddistilled yielding the following fractions:

    ______________________________________                                                                            Weight                                              Vapor   Liquid     Vacuum of                                        Fraction  Temp.   Temp.      mm/Hg. Fraction                                  No.       (°C.)                                                                          (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1         38/43    76/110    5/3    118                                       2          87     109        3.0    41                                        3          95     114        3.5    88                                        4         101     140        3.5    262                                       5         125     170        3.0    90                                        6         165     210        2.0    219                                       7         130     210        2.0    31                                        ______________________________________                                    

Fractions 2-6 are bulked and redistilled on a 12" Goodloe columnyielding the following fractions:

    ______________________________________                                                                            Weight                                              Vapor   Liquid     Vacuum of                                        Fraction  Temp.   Temp.      mm/Hg. Fractions                                 No.       (°C.)                                                                          (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1         77/86   105/110    2.5    22                                        2         86      106        2.2    22                                        3         90      108        2.2    21                                        4         87      107        2.2    26                                        5         88      108        2.2    17                                        6         91      109        2.2    27                                        7         88      108        2.2    13                                        8         89/89   112/110    2.6    20                                        9         86      110        2.6    22                                        10        85      111        1.8    23                                        11        86      113        1.8    28                                        12        86      118        1.8    22                                        13        92      126        1.8    21                                        14        92      126        1.8    15                                        ______________________________________                                    

Bulked fractions 2-12 (exo:endo ratio 55:45) has a petitgrain,neroli-like, verdima-like, green, herbaceous, and galbanum aroma withpetitgrain-like, green, ambrettseed undertones.

FIG. 1 is the GLC profile for the crude reaction product prior todistillation (Conditions: SE-30 column programmed at 100°-220° C. at 8°C. per minute).

FIG. 2 is the NMR spectrum for the resulting distillation product(Conditions: Field strength: 100 MHz; solvent: CFCl₃).

The resulting distillation product also has an excellent green bellpepper, green vegetable, galbanum-like aroma and taste at 0.1 ppmcausing it to be useful in green vegetable, bell pepper and saladdressing flavors.

EXAMPLE II Preparation of 2-(2-Norbornyl)Pyridine ##STR37##

Into a 1 liter autoclave equipped for high pressure is placed 230 gramsof the distillation product of Example I containing the compound havingthe structure: ##STR38## 230 grams of isopropyl alcohol and 7 grams ofRaney nickel. The autoclave is sealed and heated to 80° C. at 600 psigpressure, the pressure being supplied with hydrogen. The autoclave ismaintained at 600 psig and 80° C. for a period of five hours. At the endof the five hour period, the autoclave is opened and the reaction massis filtered and distilled on a splash column packed with saddlesyielding the following fractions:

    ______________________________________                                                  Vapor        Liquid  Vacuum                                         Fraction  Temp.        Temp.   mm/Hg.                                         No.       (°C.) (°C.)                                                                          Pressure                                       ______________________________________                                        1         41            44     200                                            2         35           102     1                                              3          84/          104/   1                                              ______________________________________                                    

Bulked fractions 1-3 of the resulting product has a musk, amber aromawith woody undertones. From a flavor standpoint, the resulting producthas a pear-like, peach-like and walnut-like aroma and taste profile at 5ppm.

FIG. 3 is the GLC profile of the crude reaction product (Conditions:Carbowax column programmed at 100°-220° C. at 8° C. per minute).

FIG. 4 is the NMR spectrum for fraction 1 of the above-mentioneddistillation (Conditions: Field strength: 100 MHz; solvent: CFCl₃).

EXAMPLE III Preparation of 4-Vinyl Pyridine Bicyclopentadiene Adduct##STR39##

Into a 2 liter reaction vessel equipped with reflux condenser,thermometer, heating mantle and stirrer is placed the followingmaterials:

500 grams 4-vinyl pyridine (4.76 moles)

660 grams bicyclopentadiene (5.0 moles)

10 grams Ionox®

The resulting mixture is heated to reflux at a temperature of 154°-156°C. for a period of nine hours. At the end of the nine hour reactionperiod, the reaction mass is distilled using a splash column packed withsaddles yielding the following fractions:

    ______________________________________                                                                            Weight                                              Vapor   Liquid     Vacuum of                                        Fraction  Temp.   Temp.      mm/Hg. Fraction                                  No.       (°C.)                                                                          (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1         60/54    91/122    16/10  261                                       2         104     120        3       40                                       3         107     128        3       89                                       4         108     130        3      166                                       5         112     132        3      240                                       6         120     162        3      215                                       7         170     200        3       35                                       ______________________________________                                    

Fractions 2-7 are bulked and redistilled on a 12" Goodloe columnyielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1         96/101  118/118    1.8    23                                        2        103      119        1.8    22                                        3        103      119        1.8    22                                        4        105      119        1.8    61                                        5        107      121        1.8    42                                        6        107      121        1.8    46                                        7        107      121        1.8    55                                        8        108      123        1.8    42                                        9        108      123        1.8    64                                        10       108      123        1.8    64                                        11       108      123        1.8    43                                        12       105      120        1.6    45                                        13       105      143        1.6    29                                        14       105      150        1.6    23                                        15       105      180        1.6    54                                        16       100      215        1.6    23                                        ______________________________________                                    

FIG. 5 is the GLC profile for the crude reaction product (Conditions:SE-30 column programmed at 100°-220° C. at 8° C. per minute).

FIG. 6 is the NMR spectrum for fraction 6 of the foregoing distillation(Conditions: Field strength: 100 MHz; solvent: CFCl₃).

The resulting product has an excellent woody aroma with musk, amber androse undertones. From a flavor standpoint it has an excellent pear,peach and walnut-like aroma and taste profile at 2 ppm.

EXAMPLE IV Preparation of 4-(2-Norbornyl)Pyridine ##STR40##

Into a 1 liter autoclave equipped for high pressure is placed 300 gramsof the reaction product of Example III (1.75 moles) having thestructure: ##STR41## 300 grams of anhydrous isopropyl alcohol and 6grams of Raney nickel.

The autoclave is sealed and heated to 30°-38° C. while simultaneouslybeing pressurized with hydrogen to 300 psig. The pressurization withhydrogen is maintained at 300 psig and the temperature is maintained at38°-39° C. for a period of eight hours. At the end of the eight hourperiod the autoclave is cooled and opened. The contents are filtered andthe resulting product is stripped of solvent and then distilled on asplash column packed with saddles, yielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1        50/53    55/90      300    --                                        2        23        91         3     --                                        3        100/105  118/166      1/   299                                       4        92       200        600    --                                        ______________________________________                                    

The resulting product has an excellent petitgrain aroma with rose,woody, musk and amber undertones. From a flavor standpoint, theresulting product has an excellent orange-albedo flavor at 20 ppm.

FIG. 7 is the GLC profile for the crude reaction product prior todistillation (Conditions: Carbowax column programmed at 100°-220° C. at8° C. per minute).

FIG. 8 is the NMR spectrum for the foregoing distillation product(Conditions: Field strength: 100 MHz; solvent: CFCl₃).

EXAMPLE V Preparation of 2-Vinylpyridine-Methylcyclopentadiene Adduct##STR42##

Into a 2 liter reaction flask equipped with stirrer, reflux condenser,thermometer and heating mantle are placed:

333 grams 2-vinylpyridine (2.17 moles)

673 grams methylcyclopentadiene (95%) (4.0 moles)

5 grams Ionox®

The resulting mixture is heated to reflux (163°-173° C.) and maintainedat reflux for a period of eight hours. The resultant product, 1019 gramsof crude, is charged to a still and rushed over. The rushed-over productis then fractionally distilled on a 12" Goodloe column yielding thefollowing fractions:

    ______________________________________                                                                            Weight                                              Vapor   Liquid     Vacuum of                                        Fraction  Temp.   Temp.      mm/Hg. Fraction                                  No.       (°C.)                                                                          (°C.)                                                                             Pressure                                                                             (grams)                                   ______________________________________                                        1         46/56   115/115    2.2    22                                        2         84      116        1.8    28                                        3         98      123        2.6    37                                        4         105     120        3.4    40                                        5         99      123        2.6    41                                        6         97      125        2.4    51                                        7         97      126        2.4    57                                        8         97      128        2.4    49                                        9         98      130        2.4    54                                        10        98      145        2.4    49                                        11        102     165        2.4    20                                        12        100     220        2.4    11                                        ______________________________________                                    

Fractions 5-8 are bulked and the bulked product is evaluated for itsorganoleptic properties.

FIG. 9 is the GLC profile of the crude reaction product (Conditions:SE-30 column programmed at 100°-220° C. at 8° C. per minute).

FIG. 10 is the NMR spectrum for the resulting distillation product(Conditions: Field strength: 100 MHz; solvent: CFCl₃). The resultantproduct has an excellent herbaceous, minty, green, cedarleaf-like,eucalyptus-like, citrus (bergamot) aroma profile with green, herbaceous,leafy and minty undertones. The resultant product has a fresh naturalgreen minty aroma and taste at 0.5 ppm from a food flavor standpoint.

EXAMPLE VI Preparation of 4-Vinylpyridine-Methylcyclopentadiene Adduct##STR43##

Into a 3 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle is placed the following materials:

893 grams 4-vinylpyridine (8.50 moles)

1500 grams methylcyclopentadiene (95%) (8.9 moles)

10 grams Ionox®

The resulting mixture is heated to reflux and refluxed at 173° C.-180°C. over a period of eight hours. At the end of the eight hour period,the reaction mass was cooled and placed into a short path distillationcolumn. The resulting product is rushed over and fractions 3-5 arebulked and redistilled on a 12" Goodloe column yielding the followingfractions:

    ______________________________________                                                                                Weight                                       Vapor     Liquid   Vacuum Reflux of                                    Fraction                                                                             Temp.     Temp.    mm/Hg. Ratio  Fraction                              No.    (°C.)                                                                            (°C.)                                                                           Pressure                                                                             R/D    (gms)                                 ______________________________________                                        1      35/68     106/111  1.2    9:1    16                                    2      88        120      1.0    9:1    19                                    3      92        121      1.0    8:2    47                                    4      92        121      1.0    8:2    61                                    5      92        121      1.0    8:2    60                                    6      89/97     121/128  1.2    1:1    42                                    7      93        124      1.0    1:1    44                                    8      95        127      1.0    1:1    49                                    9      105       131      1.6    1:1    61                                    10     95        128      1.1    1:1    28                                    11     95        128      1.1    1:1    48                                    12     95        130      1.0    1:1    10                                    13     96        135      1.0    1:1    43                                    14     92        150      1.1    1:1    48                                    15     92/138    165/210  1.1    1:1    46                                    ______________________________________                                    

FIG. 11 is the GLC profile for the crude reaction product prior todistillation (Conditions: SE-30 column programmed at 100°-220° C. at 8°C. per minute).

FIG. 12 is the NMR spectrum for fraction 5 of the foregoing distillationcontaining a mixture of compounds defined according to the structure:##STR44## (Conditions: Field strength: 100 MHz; solvent: CFCl₃).

The resulting product has a green, woody, cinnamon-like, orris-like andbalsamic aroma with vanoris undertones. From a flavor standpoint, it hasa cinnamon bitter chocolate aroma and taste profile at 0.1 ppm.

EXAMPLE VII

The following composition is prepared (parts by weight):

    ______________________________________                                        Ingredient           Parts by Weight                                          ______________________________________                                        Bergamot oil         120                                                      Methyl ionone        60                                                       Jasmin extra         80                                                       Petitgrain           60                                                       Patchouli oil        60                                                       Violet perfume base  60                                                       Compound having the structure:                                                                     20                                                        ##STR45##                                                                    produced according to Example I                                               Lemon oil            80                                                       Rose Geranium oil    120                                                      Lavender oil, French 120                                                      Sweet Orange Oil     80                                                       Musk extract, 3%     50                                                       Civet extract, 3%    50                                                                            960                                                      ______________________________________                                    

The addition of the compound having the structure: ##STR46## preparedaccording to Example I improves the overall quality of instantformulation lending a more petitgrain-like, neroli oil-like, verdima andgalbanum effect thereto. Overall, the formulation can be described asbergamot with petitgrain, neroli, verdima, green, herbaceous andgalbanum topnotes and amber undertones.

EXAMPLE VIII

The following composition is prepared:

    ______________________________________                                        Ingredient             Parts by Weight                                        ______________________________________                                        Linalyl acetate        135.0                                                  Bergamot oil           275.0                                                  Citronellol            135.0                                                  Lavandulol             135.0                                                  Portugal oil           135.0                                                  Neroli oil             40.5                                                   Jasmin oil             20.5                                                   Jasmin absolute        20.5                                                   Neroliol, Bigarade     28.0                                                   Rosemary oil           28.0                                                   Mixture of compounds defined according                                                               28.5                                                   to the structure:                                                              ##STR47##                                                                    prepared according to Example V                                               Rose absolute          13.5                                                   Hydroxy citronellol    13.5                                                   Cyclopentadecanolide (10% in                                                                         7.0                                                    diethyl phthalate)                                                            ______________________________________                                    

The addition of the mixture of compounds defined according to thestructure: ##STR48## prepared according to Example V in the quantitygiven adds a distinct green, herbaceous, minty, cedarleaf-like,eucalyptus-like aroma to this fragrance. In the instant example the 20.5parts of neroli oil can be replaced by 5 parts of the compound havingthe structure: ##STR49## of this invention without changing theolfactory nature or quality of the fragrance. Overall the fragrance canbe described as natural orange oil-like with green, herbaceous, minty,cedarleaf, eucalyptus-like and bergamot-like topnotes and green,herbaceous, leafy and minty undertones.

EXAMPLE IX

Perfume compositions are prepared with the following ingredients:

    ______________________________________                                                          IX(A)    IX(B)   IX(C)                                                        Parts    Parts   Parts                                                        By       By      By                                         Ingredients       Weight   Weight  Weight                                     ______________________________________                                        Vetivert oil      40       40      40                                         Sandalwood oil    100      100     100                                        Rose geranium oil 200      200     200                                        Musk extract (3%  25       25      25                                         diethyl phthalate)                                                            Civet extract (3% 25       25      25                                         diethyl phthalate)                                                            Benzyl-isoeugenol 100      100     100                                        Coumarin          100      100     100                                        Heliotropin       50       50      50                                         Bois de rose oil  200      200     200                                        Benzoin resin     100      100     100                                        Compound having the                                                                             30       0       0                                          structure:                                                                     ##STR50##                                                                    produced according to                                                         Example II                                                                    Compound having the                                                                             0        30      0                                          structure:                                                                     ##STR51##                                                                    produced according to                                                         Example III                                                                   Compound having the                                                                             0        0       30                                         structure:                                                                     ##STR52##                                                                    produced according to                                                         Example IV                                                                    ______________________________________                                    

A perfume composition exhibiting an excellent musk, amber and woodyfragrance is produced when using the formulation of Example IX(A). Whenthe compound having the structure: ##STR53## produced according toExample II is omitted the composition lacks the woody, amber fullness ofthe complete perfume composition of this example. The perfumecomposition of Example IX(A) can be described as having an intensewoody, musky, amber aroma.

The perfume composition of Example IX(B) exhibits an excellent woody,musk, amber, rose aroma. When the compound having the structure:##STR54## produced according to Example III is omitted the compositionlacks the woody, amber fullness of the complete perfume composition ofthis Example. The perfume composition of Example IX(B) can be describedas having an intense, long lasting woody, musk, amber, rose aroma.

The perfume composition of Example IX(C) exhibits an excellentpetitgrain, rose, woody, musk, amber fragrance. When the compound havingthe structure: ##STR55## produced according to Example IV, is omitted,the composition lacks the woody amber fullness of the complete perfumecomposition of Example IX(C). The composition of Example IX(C) can bedescribed as having a petitgrain, rose, woody, musk, amber fragrance.

EXAMPLE X

The following composition is prepared:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Linalyl acetate      135.0                                                    Bergamot oil         275.0                                                    Citronellol          135.0                                                    Lavandulol           135.0                                                    Portugal oil         135.0                                                    Neroli oil           40.5                                                     Jasmin oil           20.5                                                     Jasmin absolute      20.5                                                     Neroliol, Bigarade   28.0                                                     Rosemary oil         28.0                                                     Mixture of compounds defined                                                                       23.5                                                     according to the structure:                                                    ##STR56##                                                                    produced according to Example VI                                              Rose absolute        13.5                                                     Hydroxy citronellol  13.5                                                     Cyclopentadecanolide 10%                                                                           7.0                                                      ______________________________________                                    

The addition of the mixture of compounds defined according to thestructure: ##STR57## produced according to Example VI in the quantitygiven adds an excellent distinctive green, woody, cinnamon-like,orris-like, balsamic aroma to the fragrance. The fragrance can thus bedescribed as balsamic with green, woody, cinnmon-like and orris-liketopnotes and vanoris undertones.

EXAMPLE XI Preparation of a Cosmetic Powder Composition

A cosmetic powder is prepared by mixing in a ball mill, 100 grams oftalcum powder with 0.25 grams of one of the perfumery substances setforth in Table II below. Each of the cosmetic powders has an excellentintense aroma as set forth in Table II below:

                  TABLE II                                                        ______________________________________                                        Perfume Substance Perfumery Evaluation                                        ______________________________________                                        Compound having   A petitgrain-like, neroli-                                  the structure:    like, verdima-like, green,                                   ##STR58##        herbaceous, galbanum-like aroma with amber-like                               undertones.                                                 produced according to                                                         Example I                                                                     Compound having the                                                                             A musk amber aroma with                                     structure:        woody undertones.                                            ##STR59##                                                                    produced according to                                                         Example II                                                                    Compound having the                                                                             A woody aroma with musk,                                    structure:        amber and rose undertones.                                   ##STR60##                                                                    produced according to                                                         Example III                                                                   Compound having the                                                                             A petitgrain and rose                                       structure:        aroma with woody, musk and                                   ##STR61##        amber undertones.                                           produced according to                                                         Example IV                                                                    Mixture of compounds                                                                            A green, herbaceous, minty,                                 having the structure:                                                                           cedar leaf-like, eucalyp-                                    ##STR62##        tus-like and bergamot-like aroma with green, herba-                           ceous, leafy and minty nuances on dry out.                  produced according                                                            to Example V                                                                  Mixture of compounds                                                                            A green, woody, cinnamon-                                   having the structure:                                                                           like, orris-like and                                         ##STR63##        balsamic aroma with van- oris-like undertones.              produced according to                                                         Example VI                                                                    Perfume composition of                                                                          A bergamot with                                             Example VII       petitgrain, neroli, ver-                                                      dima, green, herbaceous,                                                      and galbanum topnotes and                                                     amber undertones.                                           Perfume composition of                                                                          A natural orange oil-like                                   Example VIII      with green, herbaceous,                                                       minty, cedar leaf,                                                            eucalyptus-like and                                                           bergamot-like topnotes and                                                    green, herbaceous, leafy                                                      and minty undertones.                                       Perfume composition of                                                                          An intense woody, musk,                                     Example IX(A)     amber aroma.                                                Perfume composition of                                                                          An intense, long lasting                                    Example IX(B)     woody, musk, amber, rose                                                      aroma.                                                      Perfume composition of                                                                          A petitgrain, rose, woody,                                  Example IX(C)     musk, amber fragrance.                                      Perfume composition of                                                                          A balsamic with green,                                      Example X         woody, cinnamon-like,                                                         orris-like topnotes and                                                       vanoris undertones.                                         ______________________________________                                    

EXAMPLE XII Perfumed Liquid Detergent

Concentrated liquid detergents with aromas as set forth in Table II ofExample XI (which detergents are prepared from Lysine salt of n-dodecylbenzene sulfonic acid as more specifically described in U.S. Pat. No.3,948,818 issued on Apr. 6, 1976, the specification for which isincorporated by reference herein), are prepared containing each of thesubstances set forth in Table II of Example XI, supra. They are preparedby adding and homogeneously mixing the appropriate quantity of perfumerysubstance as set forth in Table II of Example XI in the liquiddetergent. The detergents all possess aromas as set forth in Table II ofExample XI, the intensity increasing with greater concentrations ofperfumery substance of Table II of Example XI, supra.

EXAMPLE XIII Preparation of a Cologne and Handkerchief Perfume

The perfume substances of Table II of Example XI, supra, areincorporated into colognes at concentrations of 1.5%, 2.0%, 2.5%, 3.0%and 4.0% in 80%, 85% and 90% aqueous ethanols; and into handkerchiefperfume compositions at concentrations of 10%, 15%, 20%, 25%, and 30%(in 85%, 90% and 95% aqueous ethanols). Distinct and definitive aromasas set forth in Table II of Example XI are imparted to the cologne andto the handkerchief perfume compositions.

EXAMPLE XIV Preparation of a Detergent Composition

A total of a 100 grams of a detergent powder (a nonionic detergentpowder containing a proteo lytic enzyme prepared according to Example Iof Canadian Letters Patent No. 985,190 issued on Mar. 9, 1976, thedisclosure of which is incorporated by reference herein), is mixed with0.15 grams of each of the substances set forth in Table II of ExampleXI, supra, until substantially homogeneous compositions are obtained.These compositions have excellent aromas as set forth in Table II ofExample XI.

EXAMPLE XV Preparation of Soap

Each of the perfumery substances of Table II of Example XI areincorporated into soap (LVU-1) at 0.1% by weight of each substance.After two weeks in the oven at 90° F. each of the soaps showed no visualeffect from the heat. Each of the soaps manifested an excellent aroma asset forth in Table II of Example XI, supra.

EXAMPLE XVI Preparation of Soap Composition

One hundred grams of soap chips (IVORY®, registered trademark of theProcter & Gamble Co. of Cincinnati, Ohio) are mixed individually withone gram each of the perfumery substances of Table II of Example XI,supra, until a homogeneous composition is obtained. The homogeneouscomposition is then treated under three atmospheres pressure at 180° C.for a period of three hours and the resulting liquid is placed into asoap mold. The resulting soap cakes, on cooling, manifest excellentaromas as set forth in Table II of Example XI, supra.

EXAMPLE XVII Preparation of a Solid Detergent Composition

A detergent is prepared from the following ingredients according toExample I of Canadian Letters Patent No. 1,007,948 the specification forwhich is incorporated by reference herein):

    ______________________________________                                        Ingredients        Parts by Weight                                            ______________________________________                                        "Neodol 45-II" (a C.sub.14 -C.sub.15                                                             12                                                         alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                   Sodium carbonate   55                                                         Sodium citrate     20                                                         Sodium sulfate, water                                                                            q.s.                                                       brighteners                                                                   ______________________________________                                    

This detergent is a "phosphate-free" detergent. A total of 100 grams ofthis detergent is admixed separately with 0.15 grams of each of theperfume substances of Table II of Example XI, supra. The detergentsamples each have excellent aromas as set forth in Table II of ExampleXI, supra.

EXAMPLE XVIII

Utilizing the procedure of Example I at column 15 for U.S. Pat. No.3,632,396, the specification for which is incorporated by referenceherein, a non-woven cloth substrate useful as a dryer-added fabricsoftening article of manufacture is prepared wherein the substrate, thesubstrate coating and the outer coating and the perfuming material areas follows:

1. a water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.);

57 percent C₂₀₋₂₂ HAPS

22 percent isopropyl alcohol

20 percent antistatic agent

1 percent of one of the perfume substances of Table II of Example XI,supra.

A fabric softening composition prepared as set forth above having theabove aroma characteristics as set forth in Table II of Example XI,supra, essentially consists of a substrate having a weight of about 3grams per 100 square inches, a substrate coating of about 1.85 grams per100 square inches of substrate and an outer coating of about 1.4 gramsper 100 square inches of substrate, thereby providing a total aromatizedsubstrate and outer coating weight ratio of about 1:1 by weight ofsubstrate. The aroma set forth in Table II of Example XI is imparted ina pleasant manner to the headspace in the dryer on operation thereof,using said dryer-added fabric softening non-woven fabric.

EXAMPLE XIX

The following liquid flavor formulation is prepared:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Compound having the   40.0                                                    structure:                                                                     ##STR64##                                                                    prepared according to                                                         Example I                                                                     Methoxy isobutyl pyrazine                                                                           60.0                                                    prepared according to the procedure                                           of U.S. Letters Pat. No. 3,630,750                                            the specification for which is                                                incorporated by reference herein                                              ______________________________________                                    

The resulting mixture is added to a 95% food grade aqueous ethanolsolution at the rate of 3%. The resulting material is added to a "GreenGoddess® Salad Dressing" at the rate of 8 ppm of effective ingredient(that is mixture of compound having the structure: ##STR65## and methoxyisobutyl pyrazine). The addition of the compound having the structure:##STR66## to the salad dressing imparts to it an excellent natural bellpepper, green vegetable, galbanum and floral aroma and taste profile.Without the compound having the structure: although a bell pepper flavorexists in the Green Goddess® Salad Dressing flavor, it is notnatural-like and does not have the intense green vegetable characterthat is imparted thereto by the compound having the structure: ##STR67##

EXAMPLE XX Cocoa Mix

At the rate of 0.1 ppm, the mixture of compounds defined according tothe structure: ##STR68## prepared according to Example VI is added to a1.0 ounce serving of OVALTINE'S® HOT'N RICH COCOA MIX: Ingredients ofOVALTINE'S® HOT'N RICH HOT COCOA MIX:

Whey

Cocoa processed with alkali

Partially hydrogenated vegetable oil containing one or more of coconutoil, cotton seed oil, palm oil or soy bean oil

Corn syrup

Carob meal

Sugar

Tricalcium phosphate

Sodium Chloride

Sodium caseinate

Dipotassium phosphate

Sodium citrate

0.27% sodium saccharin

Propylene glycol esters of fatty acids

Sodium silico aluminate

Vanillin

Ferric sodium pyrophosphate

Carrageenan

Lecithin

Ascorbic acid

Vitamin A palmitate

Niacin

Riboflavin

Thiamin

OVALTINE'S® HOT'N RICH HOT COCOA MIX is produced by Ovaltine Products,Inc., of Villa Park, Ill. 60181.

The mixture of compounds defined according to the structure: ##STR69##prepared according to Example VI provides a cinnamon-like bitterchocolate nuance which is long lasting, intense and causes the cocoaflavor to be very natural-like.

EXAMPLE XXI

The following orange jello cake mix is prepared:

1 Box yellow cake mix

3/4 Cup orange juice

3/4 Cup Wesson oil

4 Eggs

1 Small package of orange jello

Prior to preparation, the orange juice is admixed at the rate of 0.5 ppmwith the compound having the structure: ##STR70## produced according toExample IV and at a rate of 0.5 ppm with a mixture of compounds definedaccording to the structure: ##STR71## produced according to Example V.

The resulting materials are mixed by first mixing the cake mix, orangejuice and salad oil. The eggs are added one at a time. After stirring,the jello is added. The resulting mixture is mixed thoroughly and bakedin a greased, lightly floured tube cake pan approximately one hour at350° F.

The resulting orange jello cake has an excellent natural orange flavorwith an "orange-albedo" characteristic which is reminiscent of freshlypicked oranges. The natural character, particularly the albedocharacter, is missing when the compounds having the structures:##STR72## are omitted from the cake mixture.

EXAMPLE XXIII Pineapple Nut Cake

A pyrex dish (11 inches×13 inches) is greased and spread on the bottomwith natural pineapple. Sugar is spread over the pineapple. One box ofyellow cake mix is spread over the sugar. 1.5 sticks of butter aresliced and spread over the cake mix. Two cups of pecan nuts are placedover the resulting mixture. At the rate of 1.0 ppm an aqueous ethanolic(95% ethanol) solution of a 50:50 mixture of the compounds having thestructure: ##STR73## produced according to Example II and having thestructure: ##STR74## prepared according to Example III is added by meansof sprinkling. After three minutes, the resulting product is baked at atemperature of 350° F. in an oven until the pecans almost burn. . . fora period of 45 minutes.

The resulting Pineapple Nut Cake has an excellent natural walnut tastein addition to the pineapple and pecan aroma and taste nuances. In theabsence of the compounds having the structures: ##STR75## the resultingcake is missing the natural walnut-like nuances.

EXAMPLE XXIV Raspberry Flavor Formulation

The following basic raspberry flavor formulation is produced:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Vanillin              2.0                                                     Maltol                5.0                                                     Parahydroxybenzylactone                                                                             5.0                                                     Alpha-ionone (10% in propylene glycol)                                                              2.0                                                     Ethyl butyrate        6.0                                                     Ethyl acetate         16.0                                                    Dimethyl sulfide      1.0                                                     Isobutyl acetate      13.0                                                    Acetic acid           10.0                                                    Acetaldehyde          10.0                                                    Propylene glycol      930.0                                                                         1000.0                                                  ______________________________________                                    

This formulation is divided into two portions. To the first portion amixture of compounds defined according to the structure: ##STR76##prepared according to Example V is added. To the second portion nothingis added.

The flavor containing the mixture of compounds defined according to thestructure: ##STR77## has a fresh "recently picked" raspberry aroma withraspberry kernel nuances when the mixture of compounds defined accordingto the structure: ##STR78## is added at the rate of 0.8 ppm.

The flavor containing the mixture of compounds defined according to thestructure: ##STR79## has a substantially and more pleasant and betterraspberry aroma and taste profile. It the unaminous opinion of a benchpanel of five members (not associated with the inventorship entity ofthe instant application and not associated with the assignee of theinstant application) that the mixture of compounds defined according tothe structure: ##STR80## of our invention rounds the flavor out andcontributes to a very natural fresh aroma and taste as found in fullripe raspberries which are recently picked. Accordingly, the flavor withthe addition of the mixture of compounds defined according to thestructure: is unanimously considered to be substantially better than theflavor without the mixture of compounds defined according to thestructure: ##STR81## of our invention.

EXAMPLE XXV A. Raspberry Flavor Formulation

20 Grams of the flavor formulation of Example XXIV containing themixture of compounds defined according to the structure: ##STR82##prepared according to Example V of our invention is emulsified in asolution containing 300 grams gum acacia and 700 grams of water. Theemulsion is spray-dried with a Bowen Lab Model Drier utilizing 260c.f.m. of air with an inlet temperature of 500° F. and an outlettemperature of 200° F. and a wheel speed of 50,000 rpm.

B. Sustained Release Flavor

The following mixture is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Liquid raspberry flavor of                                                                          20.00                                                   Example XXIV                                                                  Propylene Glycol      9.00                                                    Cab-O-Sil ® M-5                                                           Brand of Silica produced by                                                   125 High Street, Boston,                                                      Mass. 02110;                                                                  Physical Properties:  5.00                                                    Surface Area: 200 m.sup.2 /gm                                                 Nominal particle size: 0.012 microns                                          Density: 2.3 lbs./cu. ft.                                                     ______________________________________                                    

The Cab-O-Sil® is dispersed in each of the liquid raspberry flavorcomposition of Example XXIV (containing a mixture of compounds definedaccording to the structure: ##STR83## prepared according to Example V)with vigorous stirring, thereby resulting in a viscous liquid. 71 Partsby weight of the powder flavor composition of Part A, supra, is thenblended into the said viscous liquid, with stirring, at 25° C. for aperiod of 30 minutes, resulting in a dry, free-flowing sustained releasepowder.

EXAMPLE XXVI

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts byweight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. 20 Parts by weight of each of the liquid raspberry flavorcomposition of Example XXIV (containng a mixture of compounds definedaccording to the structure: ##STR84## prepared according to Example V)is added to solutions which are homogenized to form an emulsion having aparticle size typically in the range of 5-40 microns. The material iskept at 120° F. under which conditions the gelatin will not jell.

Coacervation is induced by adding slowly and uniformly, 40 parts byweight of a 20% aqueous solution of sodium sulphate. During coacervationthe gelatin molecules are deposited uniformly about each oil droplet asa nucleus.

Gelatin is effected by pouring the heated coacervate mixture into 1,000parts by weight of 7% aqueous solution of sodium sulphate at 65° C. Theresulting jelled coacervate may be filtered and washed with water attemperatures below the melting point of gelatin, to remove the salt.

Hardening of the filtered cake, in this example is effected by washingwith 200 parts by weight of 37% solution of formaldehyde in water. Thecake is then washed to remove residual formaldehyde.

EXAMPLE XXVII Chewing Gum

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example XXVI. 300 Parts of sucroseand 100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blends are then manufactured into strips 1inch in width and 0.1 of an inch in thickness. The strips are cut intolengths of 3 inches each. On chewing, the chewing gum has a pleasant,long-lasting raspberry flavor.

EXAMPLE XXVIII Chewing Gum

100 Parts by weight of chicle are mixed with 18 parts by weight of theflavors prepared in accordance with Example XXV(B). 300 Parts of sucroseand 100 parts of corn syrup are then added. Mixing is effected in aribbon blender with jacketed walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blends are then manufactured into strips 1inch in width and 0.1 of an inch in thickness. The strips are cut intolengths 3 inches each. On chewing, the chewing gum has a pleasant,long-lasting raspberry flavor.

EXAMPLE XXIX Toothpaste Formulation

The following separate groups of ingredients are prepared:

    ______________________________________                                        Ingredient         Parts by Weight                                            ______________________________________                                        Group "A"                                                                     Glycerine          30.200                                                     Distilled Water    15.325                                                     Sodium Benzoate     .100                                                      Saccharin Sodium    .125                                                      Stannous            .400                                                      Group "B"                                                                     Calcium Carbonate  12.500                                                     Dicalcium Phosphate                                                                              37.200                                                     (Dihydrate)                                                                   Group "C"                                                                     Sodium N--Lauroyl   2.000                                                     Sarcosinate (foaming agent)                                                   Group "D"                                                                     Flavor Material of  1.200                                                     Example XXV(B)                                                                TOTAL              100.000                                                    ______________________________________                                    

Procedure

1. The ingredients in Group "A" are stirred and heated in a steamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogeneous gel.

3. The powders of Group "B" are added to the gel, while mixing, until ahomogeneous paste is formed.

4. With stirring, the flavor of "D" is added and lastly the sodiumn-laurate sarcasinate.

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to a three roller mill and then homogenized,and finally tubed.

The resulting toothpaste, when used in a normal toothbrushing procedureyields a pleasant raspberry flavor, of constant strong intensitythroughout said procedure (1-1.5 minutes).

EXAMPLE XXX Chewable Vitamin Tablets

The flavor material produced according to the procedure of ExampleXXV(B) is added to a chewable vitamin tablet formulation at a rate of 10gm/kg, which chewable vitamin tablet formulation is prepared as follows:

In a Hobart Mixer, the following materials are blended to homogeneity:

    ______________________________________                                        Ingredient           Gms/1000 Tablets                                         ______________________________________                                        Vitamin C (ascorbid acid)                                                                          7.000                                                    as ascorbic acid-sodium                                                       asorbate mixture 1:1                                                          Vitamin B.sub.1 (thiamine mononitrate)                                                             4.000                                                    as Rocoat ® thiamine mononitrate                                          331/3% (Hoffman La Roche                                                      Vitamin B.sub.2 (riboflavin) as                                                                    5.000                                                    Rocoat ® riboflavin 331/3%                                                Vitamin B.sub.6 (pyridoxine hydrochloride)                                                         4.000                                                    as Rocoat ® pyridoxine hydrochloride                                      331/3%                                                                        Niacinamide as Rocoat ® niacinamide                                                            33.000                                                   331/3%                                                                        Calcium pantothenate 11.500                                                   Vitamin B.sub.12 (cyanocobalamin) as                                                               3.500                                                    Merck 0.1% in gelatin                                                         Vitamin E (di-alpha tocopheryl acetate)                                                            6.600                                                    as dry Vitamin E acetate 331/3%                                               d-Biotin             0.044                                                    Flavor of Example XXV(B)                                                                           (as indicated                                                                 above)                                                   Certified lake color 5.000                                                    Sweetener - sodium saccharin                                                                       1.000                                                    Magnesium stearate lubricant                                                                       10.000                                                   Mannitol q.s. to make                                                                              500.000                                                  ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 Grams dry Vitamin A Acetate and 0.6grams Vitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 grams each.

EXAMPLE XXXI Chewing Tobacco

Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15%Pennsylvania leaf) the following casing is sprayed at the rate of 30%:

    ______________________________________                                        Ingredient          Parts by Weight                                           ______________________________________                                        Corn syrup          60.0                                                      Licorice            10.0                                                      Glycerine           20.0                                                      Fig Juice            4.6                                                      Raspberry flavor formulation                                                                       5.0                                                      of Example XXV(B)                                                             ______________________________________                                    

The resultant product is redried to a moisture content of 20%. Onchewing, this tobacco has an excellent substantially consistent,long-lasting raspberry-like nuance, in conjunction with the tobacconotes.

EXAMPLE XXXII

Crest® toothpaste (ordinary flavor) manufactured by the Proctor & GambleCo. of Cincinnati, Ohio, is intimately mixed at the rate of 1 ppm with amixture of compounds defined according to the structure: ##STR85##produced according to Example V. The resulting toothpaste on brushinggives rise to a fresh, natural, green, minty, natural orange tasteprofile which lasts during the entire brushing sequence (approximatelytwo minutes).

What is claimed is:
 1. A process for augmenting or enhancing the aromaof a consumable material selected from the group consisting of perfumecompositions, colognes and perfumed articles comprising the step ofadding to said consumable material an aroma augmenting or enhancingquantity of at least one product produced according to the process ofintimately admixing a compound defined according to the structure:##STR86## wherein one of R₁ or R₂ is vinyl and the other R₁ or R₂ ishydrogen with the compound having the structure: ##STR87## wherein oneof R₃, R₃ ', R₃ ", R₃ '" and R₃ "" is methyl and the other of R₃, R₃ ',R₃ ", R₃ '" and R₃ "" represents hydrogen and wherein one of R₄, R₄ ',R₄ ", R₄ '" and R₄ "" represents methyl and the other of R₄, R₄ ', R₄ ",R₄ '" and R₄ "" represents hydrogen and heating the resulting mixture toreflux whereby the reaction: ##STR88## is carried out, thereby forming amixture of compounds defined according to the structure: ##STR89##wherein one of R₅, R₅ ', R₅ ", R₅ '" and R₅ "" is methyl and the otherof R₅, R₅ ', R₅ ", R₅ '" and R₅ "" is hydrogen.
 2. A process foraugmenting or enhancing the aroma of a consumable material selected fromthe group consisting of perfume compositions, colognes and perfumedarticles comprising the step of adding to said consumable material anaroma augmenting or enhancing quantity of at least one pyridinylderivative defined according to the structure: ##STR90## wherein R₅, R₅', R₅ ", R₅ '" and R₅ "" represent hydrogen or methyl; wherein thedashed line represents a carbon-carbon single bond or a carbon-carbondouble bond; and wherein the norbornyl moiety is bonded to the pyridinylmoiety at the 2' position of the norbornyl moiety and the 2 or the 4position of the pyridinyl moiety; with the proviso that the substanceadded to the consumable material is a mixture when one of R₅, R₅ ', R₅", R₅ '" or R₅ "" is methyl.
 3. The process of claim 2 wherein thepyridinyl derivative is a mixture of compounds having the structures:##STR91##
 4. The process of claim 2 wherein the pyridinyl derivative isa mixture of compounds having the structures: ##STR92##
 5. The processof claim 2 wherein the pyridinyl derivative has the structure: ##STR93##6. The process of claim 2 wherein the pyridinyl derivative has thestructure: ##STR94##
 7. The process of claim 2 wherein the pyridinylderivative has the structure: ##STR95##
 8. The process of claim 2wherein the pyridinyl derivative has the structure: ##STR96##